Unveiling the Electronic Structure of Pseudotetragonal WO3 Thin Films.

WO3 is a 5d compound that undergoes several structural transitions in its bulk form. Its versatility is well-documented, with a wide range of applications, such as flexopiezoelectricity, electrochromism, gating-induced phase transitions, and its ability to improve the performance of Li-based batteries. The synthesis of WO3 thin films holds promise in stabilizing electronic phases for practical applications. However, despite its potential, the electronic structure of this material remains experimentally unexplored. Furthermore, its thermal instability limits its use in certain technological devices. Here, we employ tensile strain to stabilize WO3 thin films, which we call the pseudotetragonal phase, and investigate its electronic structure using a combination of photoelectron spectroscopy and density functional theory calculations. This study reveals the Fermiology of the system, notably identifying significant energy splittings between different orbital manifolds arising from atomic distortions. These splittings, along with the system's thermal stability, offer a potential avenue for controlling inter- and intraband scattering for electronic applications.

Anisotropic hybridization probed by polarization dependent x-ray absorption spectroscopy in VI3van der Waals Mott ferromagnet.

Polarization dependent x-ray absorption spectroscopy was used to study the magnetic ground state and the orbital occupation in bulk-phase VI3van der Waals crystals below and above the ferromagnetic and structural transitions. X-ray natural linear dichroism and x-ray magnetic circular dichroism spectra acquired at the VL2,3edges are compared against multiplet cluster calculations within the frame of the ligand field theory to quantify the intra-atomic electronic interactions at play and evaluate the effects of symmetry reduction occurring in a trigonally distorted VI6unit. We observed a non zero linear dichroism proving the presence of an anisotropic charge density distribution around the V3+ion due to the unbalanced hybridization between the vanadium and the ligand states. Such hybridization acts as an effective trigonal crystal field, slightly lifting the degeneracy of thet2g2ground state. However, the energy splitting associated to the distortion underestimates the experimental band gap, suggesting that the insulating ground state is stabilized by Mott correlation effects rather than via a Jahn-Teller mechanism. Our results clarify the role of the distortion in VI3and establish a benchmark for the study of the spectroscopic properties of other van der Waals halides, including emerging 2D materials with mono and few-layers thickness, whose fundamental properties might be altered by reduced dimensions and interface proximity.

Dual pulsed laser deposition system for the growth of complex materials and heterostructures.

Here, we present an integrated ultra-high-vacuum (UHV) apparatus for the growth of complex materials and heterostructures. The specific growth technique is the Pulsed Laser Deposition (PLD) by means of a dual-laser source based on an excimer KrF ultraviolet and solid-state Nd:YAG infra-red lasers. By taking advantage of the two laser sources-both lasers can be independently used within the deposition chambers-a large number of different materials-ranging from oxides to metals, to selenides, and others-can be successfully grown in the form of thin films and heterostructures. All of the samples can be in situ transferred between the deposition chambers and the analysis chambers by using vessels and holders' manipulators. The apparatus also offers the possibility to transfer samples to remote instrumentation under UHV conditions by means of commercially available UHV-suitcases. The dual-PLD operates for in-house research as well as user facility in combination with the Advanced Photo-electric Effect beamline at the Elettra synchrotron radiation facility in Trieste and allows synchrotron-based photo-emission as well as x-ray absorption experiments on pristine films and heterostructures.

Tomographic mapping of the hidden dimension in quasi-particle interference.

Quasiparticle interference (QPI) imaging is well established to study the low-energy electronic structure in strongly correlated electron materials with unrivalled energy resolution. Yet, being a surface-sensitive technique, the interpretation of QPI only works well for anisotropic materials, where the dispersion in the direction perpendicular to the surface can be neglected and the quasiparticle interference is dominated by a quasi-2D electronic structure. Here, we explore QPI imaging of galena, a material with an electronic structure that does not exhibit pronounced anisotropy. We find that the quasiparticle interference signal is dominated by scattering vectors which are parallel to the surface plane however originate from bias-dependent cuts of the 3D electronic structure. We develop a formalism for the theoretical description of the QPI signal and demonstrate how this quasiparticle tomography can be used to obtain information about the 3D electronic structure and orbital character of the bands.

A multicenter validation of the revised version of the Milan system for reporting salivary gland cytology (MSRSGC).

INTRODUCTION: Fine-needle aspiration cytology (FNAC) is a basic step in the diagnosis of salivary gland tumors that have a wide variety of histological types. The recent Milan system for reporting salivary gland cytopathology (MSRSGC) can correlate the risk of malignancy with precise cytological features. A revised version was recently proposed to improve the surgical relevance and facilitate uniform management. MATERIAL AND METHODS: A multicenter study retrospectively used the original and revised MSRSGC criteria to classify a series of patients who received surgery after FNAC. RESULTS: We enrolled 503 patients from three tertiary centers. The risk of malignancy for the MSRSGC resulted 19.5% in cat. I, 14.3% in cat. II, 17.6% in cat. III, 3.6% in cat. IVa, 24.6% in cat. IVb, 66.7% in cat. V, and 96.8% in cat. VI. The results from the revised MSRSGC were consistent with the original values. CONCLUSION: The MSRSGC is a promising classification system. In our opinion, the revised version of the MSRSGC supplements FNAC with some crucial clinical information and can better identify the appropriate treatment in each category.

Probing spin correlations using angle-resolved photoemission in a coupled metallic/Mott insulator system.

A nearly free electron metal and a Mott insulating state can be thought of as opposite ends of the spectrum of possibilities for the motion of electrons in a solid. Understanding their interaction lies at the heart of the correlated electron problem. In the magnetic oxide metal PdCrO2, nearly free and Mott-localized electrons exist in alternating layers, forming natural heterostructures. Using angle-resolved photoemission spectroscopy, quantitatively supported by a strong coupling analysis, we show that the coupling between these layers leads to an "intertwined" excitation that is a convolution of the charge spectrum of the metallic layer and the spin susceptibility of the Mott layer. Our findings establish PdCrO2 as a model system in which to probe Kondo lattice physics and also open new routes to use the a priori nonmagnetic probe of photoemission to gain insights into the spin susceptibility of correlated electron materials.

The occupied electronic structure of ultrathin boron doped diamond.

Using angle-resolved photoelectron spectroscopy, we compare the electronic band structure of an ultrathin (1.8 nm) δ-layer of boron-doped diamond with a bulk-like boron doped diamond film (3 µm). Surprisingly, the measurements indicate that except for a small change in the effective mass, there is no significant difference between the electronic structure of these samples, irrespective of their physical dimensionality, except for a small modification of the effective mass. While this suggests that, at the current time, it is not possible to fabricate boron-doped diamond structures with quantum properties, it also means that nanoscale boron doped diamond structures can be fabricated which retain the classical electronic properties of bulk-doped diamond, without a need to consider the influence of quantum confinement.

Weyl-like points from band inversions of spin-polarised surface states in NbGeSb.

Band inversions are key to stabilising a variety of novel electronic states in solids, from topological surface states to the formation of symmetry-protected three-dimensional Dirac and Weyl points and nodal-line semimetals. Here, we create a band inversion not of bulk states, but rather between manifolds of surface states. We realise this by aliovalent substitution of Nb for Zr and Sb for S in the ZrSiS family of nonsymmorphic semimetals. Using angle-resolved photoemission and density-functional theory, we show how two pairs of surface states, known from ZrSiS, are driven to intersect each other near the Fermi level in NbGeSb, and to develop pronounced spin splittings. We demonstrate how mirror symmetry leads to protected crossing points in the resulting spin-orbital entangled surface band structure, thereby stabilising surface state analogues of three-dimensional Weyl points. More generally, our observations suggest new opportunities for engineering topologically and symmetry-protected states via band inversions of surface states.

Fermiology and Superconductivity of Topological Surface States in PdTe_{2}.

We study the low-energy surface electronic structure of the transition-metal dichalcogenide superconductor PdTe_{2} by spin- and angle-resolved photoemission, scanning tunneling microscopy, and density-functional theory-based supercell calculations. Comparing PdTe_{2} with its sister compound PtSe_{2}, we demonstrate how enhanced interlayer hopping in the Te-based material drives a band inversion within the antibonding p-orbital manifold well above the Fermi level. We show how this mediates spin-polarized topological surface states which form rich multivalley Fermi surfaces with complex spin textures. Scanning tunneling spectroscopy reveals type-II superconductivity at the surface, and moreover shows no evidence for an unconventional component of its superconducting order parameter, despite the presence of topological surface states.

Simultaneous Conduction and Valence Band Quantization in Ultrashallow High-Density Doping Profiles in Semiconductors.

We demonstrate simultaneous quantization of conduction band (CB) and valence band (VB) states in silicon using ultrashallow, high-density, phosphorus doping profiles (so-called Si:P δ layers). We show that, in addition to the well-known quantization of CB states within the dopant plane, the confinement of VB-derived states between the subsurface P dopant layer and the Si surface gives rise to a simultaneous quantization of VB states in this narrow region. We also show that the VB quantization can be explained using a simple particle-in-a-box model, and that the number and energy separation of the quantized VB states depend on the depth of the P dopant layer beneath the Si surface. Since the quantized CB states do not show a strong dependence on the dopant depth (but rather on the dopant density), it is straightforward to exhibit control over the properties of the quantized CB and VB states independently of each other by choosing the dopant density and depth accordingly, thus offering new possibilities for engineering quantum matter.

Ubiquitous formation of bulk Dirac cones and topological surface states from a single orbital manifold in transition-metal dichalcogenides.

Transition-metal dichalcogenides (TMDs) are renowned for their rich and varied bulk properties, while their single-layer variants have become one of the most prominent examples of two-dimensional materials beyond graphene. Their disparate ground states largely depend on transition metal d-electron-derived electronic states, on which the vast majority of attention has been concentrated to date. Here, we focus on the chalcogen-derived states. From density-functional theory calculations together with spin- and angle-resolved photoemission, we find that these generically host a co-existence of type-I and type-II three-dimensional bulk Dirac fermions as well as ladders of topological surface states and surface resonances. We demonstrate how these naturally arise within a single p-orbital manifold as a general consequence of a trigonal crystal field, and as such can be expected across a large number of compounds. Already, we demonstrate their existence in six separate TMDs, opening routes to tune, and ultimately exploit, their topological physics.

Maximal Rashba-like spin splitting via kinetic-energy-coupled inversion-symmetry breaking.

Engineering and enhancing the breaking of inversion symmetry in solids-that is, allowing electrons to differentiate between 'up' and 'down'-is a key goal in condensed-matter physics and materials science because it can be used to stabilize states that are of fundamental interest and also have potential practical applications. Examples include improved ferroelectrics for memory devices and materials that host Majorana zero modes for quantum computing. Although inversion symmetry is naturally broken in several crystalline environments, such as at surfaces and interfaces, maximizing the influence of this effect on the electronic states of interest remains a challenge. Here we present a mechanism for realizing a much larger coupling of inversion-symmetry breaking to itinerant surface electrons than is typically achieved. The key element is a pronounced asymmetry of surface hopping energies-that is, a kinetic-energy-coupled inversion-symmetry breaking, the energy scale of which is a substantial fraction of the bandwidth. Using spin- and angle-resolved photoemission spectroscopy, we demonstrate that such a strong inversion-symmetry breaking, when combined with spin-orbit interactions, can mediate Rashba-like spin splittings that are much larger than would typically be expected. The energy scale of the inversion-symmetry breaking that we achieve is so large that the spin splitting in the CoO2- and RhO2-derived surface states of delafossite oxides becomes controlled by the full atomic spin-orbit coupling of the 3d and 4d transition metals, resulting in some of the largest known Rashba-like spin splittings. The core structural building blocks that facilitate the bandwidth-scaled inversion-symmetry breaking are common to numerous materials. Our findings therefore provide opportunities for creating spin-textured states and suggest routes to interfacial control of inversion-symmetry breaking in designer heterostructures of oxides and other material classes.

Spin-valley locking in the normal state of a transition-metal dichalcogenide superconductor.

Metallic transition-metal dichalcogenides (TMDCs) are benchmark systems for studying and controlling intertwined electronic orders in solids, with superconductivity developing from a charge-density wave state. The interplay between such phases is thought to play a critical role in the unconventional superconductivity of cuprates, Fe-based and heavy-fermion systems, yet even for the more moderately-correlated TMDCs, their nature and origins have proved controversial. Here, we study a prototypical example, 2H-NbSe2, by spin- and angle-resolved photoemission and first-principles theory. We find that the normal state, from which its hallmark collective phases emerge, is characterized by quasiparticles whose spin is locked to their valley pseudospin. This results from a combination of strong spin-orbit interactions and local inversion symmetry breaking, while interlayer coupling further drives a rich three-dimensional momentum dependence of the underlying Fermi-surface spin texture. These findings necessitate a re-investigation of the nature of charge order and superconducting pairing in NbSe2 and related TMDCs.

WldS can delay Wallerian degeneration in mice when interaction with valosin-containing protein is weakened.

Axon degeneration is an early event in many neurodegenerative disorders. In some, the mechanism is related to injury-induced Wallerian degeneration, a proactive death program that can be strongly delayed by the neuroprotective slow Wallerian degeneration protein (Wld(S)) protein. Thus, it is important to understand the Wallerian degeneration mechanism and how Wld(S) blocks it. Wld(S) location is influenced by binding to valosin-containing protein (VCP), an essential protein for many cellular processes including membrane fusion and endoplasmic reticulum-associated degradation. In mice, the N-terminal 16 amino acids (N16), which mediate VCP binding, are essential for Wld(S) to protect axons, a role which another VCP binding sequence can substitute. In Drosophila, the Wld(S) phenotype is weakened by a similar N-terminal truncation and by knocking down the VCP homologue ter94. Neither null nor floxed VCP mice are viable so it is difficult to confirm the requirement for VCP binding in mammals in vivo. However, the hypothesis can be tested further by introducing a Wld(S) missense mutation, altering its affinity for VCP but minimizing the risk of disturbing other aspects of its structure or function. We introduced the R10A mutation, which weakens VCP binding in vitro, and expressed it in transgenic mice. R10AWld(S) fails to co-immunoprecipitate VCP from mouse brain, and only occasionally and faintly accumulates in nuclear foci for which VCP binding is necessary but not sufficient. Surprisingly however, axon protection remains robust and indistinguishable from that in spontaneous Wld(S) mice. We suggest that either N16 has an additional, VCP-independent function in mammals, or that the phenotype requires only weak VCP binding which may be driven forwards in vivo by the high VCP concentration.

Fistula in ano: anatomoclinical aspects, surgical therapy and results in 844 patients.

BACKGROUND: Several new therapies, including advancement flaps and fibrin glue, have been proposed for fistula in ano, with conflicting results. Most colorectal surgeons continue to use classic methods, e.g. fistulotomy, fistulectomy, a combined method, loose or cutting seton, and rubber loop. The aim of the present study is to report the outcome of our patients, operated on by such methods. METHODS: We retrospectively reviewed the clinical records of 844 patients treated for anal fistula over a 30-year period, and assessed fistula morphology, surgical procedure and healing period. For patients treated 2 or more years prior to this study, we evaluated rates of persistent fistula and relapse, as well as prevalence of incontinence and patient satisfaction. RESULTS: The majority of patients had trans-sphincteric fistulae (58.3%). We observed 274 secondary extensions (32.5%); these were common in all fistula types except for intrasphincteric fistulae. Most patients were treated by fistulotomy alone (594 patients, 70.4%) or by the combined fistulectomy-fistulotomy method (237 patients, 28.1%), with or without loose seton. All patients with trans-, supra- and extrasphincteric fistulae were re-examined in the operations theatre. Follow-up data were available for 652 (87%) of 751 patients at least two years after surgery. The anal fistula persisted in 3.2% and recurred in 2.1% of cases. A second procedure lowered the initial rate of unsuccessful operations from 5.3% to 2.5%. Continence disorders were reported in 6.9% of patients: 4.0% complained of incontinence to gas, 2.6% to liquid and 0.3% to solid feces. CONCLUSIONS: Fistulotomy and fistulectomy with loose seton supported by preoperative anal manometry and postoperative evaluation under anaesthesia are followed by good clinical and functional results.

Submucosal reconstructive hemorrhoidectomy (Parks' operation): a 20-year experience.

BACKGROUND: Submucosal reconstructive hemorrhoidectomy has never been a popular operation due to its difficulty and duration, the amount of blood loss, and the risk of incontinence. The main indication for hemorrhoidectomy according to Parks is fourth-degree hemorrhoids with prolapse of the dentate line outside the anus and with simultaneous presence of external hemorrhoids. We report our experience in the treatment of hemorrhoids using submucosal reconstructive hemorrhoidectomy according to Parks. METHODS: A total of 640 patients (381 men and 259 women) of median age 42 years (range, 18-81) were treated between 1983 and 2002; 80% of patients had fourth-degree, 19% third-degree and 1% second- degree hemorrhoids. All patients underwent rectosigmoidoscopic examination before surgery; patients over 35 years of age or with a suspected inflammatory or neoplastic disease underwent colonoscopy or barium enema. All patients underwent anorectal manometry before operation, to measure anal resting pressure, maximal squeeze and sphincter length, with the purpose of determining if an internal sphincterotomy was also necessary (in case of high anal resting tone). One-third of the patients also had an internal sphincterotomy to correct anal hypertonia. RESULTS: Postoperative bleeding occurred in 19 patients (2.9%), 0.9% requiring a reintervention. Severe pain was reported by 9 patients (1.4%); fecal impaction occurred in 3 cases (0.5%) and suture disruption in 2 patients (0.3%). In 74 patients (11.6%), bladder catheterization was needed due to urinary retention. Of 550 patients who had a minimum follow-up of 3 years and were sent a postal questionnaire, 374 patients responded, with a median 7.3-year follow- up; 176 patients (32%) were lost to follow-up. Eleven patients (2.9% of 374 cases) reported pain during defecation, 6 (1.6%) developed skin tags or recurrence, 3 (0.8%) reported gas incontinence, 2 (0.5%) developed anal fistula and 1 (0.3%) had anal stricture. CONCLUSIONS: Submucosal reconstructive hemorrhoidectomy according to Parks still represents a good choice for the treatment of high-degree hemorrhoids with prolapse of the dentate line outside the anus and external circumferential hemorrhoids.

Synthesis and biological evaluation of NAD analogs as human pyridine nucleotide adenylyltransferase inhibitors.

NAD analogs modified at the ribose adenylyl moiety, named N-2'-MeAD and Na-2'-MeAD, were synthesized as ligands of pyridine nucleotide (NMN/NaMN) adenylyltransferase (NMNAT). Both dinucleotides resulted selective inhibitors against human NMNAT-3 isoenzyme.

Calibrated lateral internal sphincterotomy for chronic anal fissure.

UNLABELLED: Lateral internal sphincterotomy is an effective procedure for the treatment of anal fissure, but may affected anal continence. We describe a procedure aimed at tailoring the division of the sphincter according to the degree of the hypertonia and to the sphincter length in order to offer an effective and safe treatment for chronic anal fissure. METHODS: The internal sphincter was divided on the basis of anal manometry results. The average of maximum values of resting pressure determined by the stationary motility protocol was considered the reference parameter to measure hypertonia. Mild hypertone was considered to be 50-60 mmHg, moderate hypertone 60-80 mmHg, and severe hypertone >80 mmHg. In case of mild hypertone, 20% of the internal sphincter was divided; in case of moderate hypertone; 40% and 60% for severe hypertone. Calibrated lateral internal sphincterotomy is the division of the internal sphincter based on these parameters. Over 5 years, 388 patients underwent this procedure (197 men, 191 women) with a median age of 43 years (range, 18-80). RESULTS: Postoperative complications consisted of abscess in 4 patients (1.0%), hemorrhage in 2 patients (0.5%), and pain in 6 patients (1.5%). Follow-up data are available for 261 patients (67.3%). Two months after surgery, 9 patients (3.4%) complained of persistent or recurring pain with or without fissure and 1 (0.4%) complained of gas incontinence. At postoperative manometry, 12 patients (4.6%) revealed persistence of anal resting pressure over 40 mmHg, 9 patients (3.4%) were still symptomatic and 97.6% were cured at a median follow-up of 8 months. An anal resting pressure lower than 30 mmHg was found in 10 patients (3.8%), only one of whom was incontinent. CONCLUSIONS: Calibrated sphincterotomy may represent an effective and safe procedure for the treatment of chronic anal fissure.